Epoxidized 4-methylenecyclohexanemethyl esters and resins therefrom



United States Patent 3,288,814 EPOXIDIZED 4 METHYLENECYCLOHEXANE- METHYL ESTERS AND RESltNS THEREFBOM Wayne V. McConnell and William H. Moore, Kingsport,

Tenn., assignors to Eastman Kodak Company, Rochester, N .Y., a corporation of New Jersey No Drawing. Filed Nov. 7, 1962, Ser. No. 236,136 11 Claims. (Cl. 260-348) This invention relates to a new class of epoxides, to resins prepared therefrom, and to the production of these compounds.

The new epoxides of the invention may be represented by the following general structures:

I R(COOA), II 1( )n III R2( )2 IV R (COOA) V 4( )2 and wherein each n represents an integer of from 2-4, each A represents the group:

CHr-CHz CH2CH C-CH2 CHz-CHz O R represents a polyvalent benzene nucleus, R represents a polyvalent cyclohexane nucleus, R represents a divalent cyclohexane nucleons containing an epoxy group on vicinal ring carbons, for example, a 7-oxabicyclo[4.l.0]heptane nucleus, R represents a divalent alkylene group of from 2-12 carbon atoms, e.g. C H.,, C I -I C H C H etc. groups, R represents a divalent alkylene group of from 2-8 carbon atoms interrupted by an O-- linkage, i.e. a group represented by R OR wherein each R contains from 1-4 carbon atoms such as etc. groups, and R represents the group CI- I=CH- in either cis or transforms. The above defined epoxides are all useful as plasticizers and stabilizers for various polymeric materials, eg for halogen-containing polymers such as poly(vinyl chloride) and for cellulose esters such as cellulose acetate butyra-te. They also constitute an especially useful class of intermediates for the production of a Wide range of epoxy resins which are especially adapted for use as adhesives, laminates, and for coating and encapsulating applications and-casting.

It is, accordingly, an object of the invention to provide a new class of epoxide monomers. Another object is to provide epoxy resins therefrom. Another object is to provide processes for preparing the above compounds. Other objects will become apparent from the description and examples.

In accordance with the invention, we prepare our new epoxides by the epoxidation of esters prepared from 4- rnethylenecyclohexanemethan01 of the structure:

G HP 0 H OH-CHzOH C Hz-CHg and appropriate polybasic acids. The reactions may be illustrated by the following general equations:

"ice

ESTERIF ICATION /CH2OH R(OOOH),. nHOCHzCH C=CH2 GHQ-CH2 CH2OH2 moooonlon, 0:01am

CHz-CH EPOXIDATION CH2CH2 R(OOOOH1GH C=CH2)n Peracid CH2CH2 CHz-CH:

R(COOCH 2OH CCH2)n CHz-CHz 0 It Will be understood that R can be substituted in the above equations by R R R R or R all of which have been previously defined. The esterification step is preferably carried out by heating a mixture of the alcohol and the acid using titanium alcoholates as catalysts, preferably titanium butoxide. The alcohol is used in amount equal to or slightly in excess of that required to esterify all of the carboxylic groups, i.e. approximately 1 mole of the alcohol for each carboxylic group. The amount of the catalyst can vary from about 0.0052% based on the total weight of the alcohol and acid. Advantageously, the reaction is conducted in a high-boiling inert solvent medium, for example, in xylene. The ester product can then be recovered by conventional separation means. The 4- methylenecyclohexanedimethanol may be prepared by the pyrolysis of 1,4-cyclohexanedimethanol or of a diester of this diol. Reference may also be had to the procedure described by G. A. Haggis et al., J. Chem. Soc., 1953, pages 404-407, for preparing the above intermediate. For the epoxidation step, a percarboxylic acid such as perpropionic acid, perbutyric acid, perbenzoic acid, etc., is employed, but preferably peracetic acid in an amount of approximately -1 mole of the acid per methylene group contained in the ester to be epoxidized. The peracetic acid is added dropwise to the ester, which is maintained at a temperature of from 2550 C. An inert solvent, for example such as chloroform, may be used with advantage as the reaction medium. The epoxide products are recovered from the reaction mixture by washing with water and distilling off the low-boiling materials under reduced pressure.

Suitable polybasic acids for the esterification step with the 4-methylenecyclohexanemethanol include those of the general formulas R (COOH),,, R (COOH) R (COOH) R (CO OH) and R (COOH) for example, aromatic acids, for example, or-thophthalic, trimellitic, pyromellitic, etc. acids,'alicyclic acids such as, for

example, 1,2-cyclohexanedicarboxylic, 1,4-cyclohexanedicarboxylic, 1,2,3-cyclohexauetricarboxylic, 1,2,3,4-cyclohexanetetracarboxylic, 4,5-epoxy 1,2 cyclohexanedicarboxylic, etc. acids, al-kanedioic acids such as, for example, oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, sebacic, dodecandioic, etc. acids, dibasic ether acids, such as for example, diglycolic, etc. acids, and alkenedioic acids such as, for example, maleic and fumaric acids. The polybasic acids can be used as convenient in their free acid or anhydride forms or in some cases as lower alkyl esters or acid chlorides thereof.

To obtain the epoxy resins of the invention, the epoxides prepared as above described are heated with amines or with acid anhydrides. Useful resin compositions are obtained with amines when the epoxide compound is mixed 3 4 in such proportions as to provide from 0.7 to 2.0 amino tanium compounds and tin compounds which are effective hydrogens for each epoxy group of the epoxide. With in catalyzing this reaction are well known to those skilled anhydrides, useful compositions are obtained from mixin the art. Azeotroping solvents other than Xylene can tures containing from 0.5 to 3.0 anhydride carbonyl groups be used or the reaction may be carried out in the absence for each epoxy group. A polyol is customarily employed 5 of solvents. Thus, the phthalic anhydride in the above with the anhydride in an amount of about from 12%, examples can be substituted in like or equivalent amount based on the total weight of the epoxide compound and by any of the polybasic acids mentioned as being suitable the anhydride. Well known anhydrides that are useful in the above esterification process. Thus, terephthalic, in forming the above resins include phthalic, tetrahydrotrimellitic, pyrornellitic, adipic, 1,2-cyclohexancdicarboxphthalic, 1,2-cyclohexanedicarboxylic anhydrides, etc., ylic, 4,5-epoxy-1,2-cyclohexanedicarboxylic, fumaric, and chlorinated derivatives of phthalic anhydride. Monomaleic, etc. acids, for example, will give the correspondand dibasic acids may also be used in the resin making ing ester products. compositions in place of the hydroxy compounds and the It is understood that the familiar ester interchange anhydrides. The properties of the resin may be modified reactions are also suitable, and are sometimes preferable by curing or postcuring at temperatures from about 50- for the preparation of the unsaturated esters. This is 200 C., or by varying the ratios of the resin components. illustrated, for example, by the reaction of dimethyl Suitable polyols include any of the known diols, triols, terephthalate with 4-methylenecyclohexanemethanol in etc., for example ethylene glycol, trimethylene glycol, the presence of catalysts such as those described above to tetramethylene glycol, pentamethylene glycol, ;l,2,6-hexgive the desired unsaturated ester.

Example 2.Diep0xide of 4-methylenecyclohexanemethyl terephthalate CH2GH3 GHQ-CH2 0H=o CHOH2OC-COCHzOH G-CHa I) ll O GHQ-CH2 O O CH2CH2 0 anetriol, cyclohexanedimethanol, pentaerythritol, and the A mixture of 4-methylenecyclohexanemethyl terephthalike. Suitable polyamines include ethylenediamine, hexalate (38 g., 0.1 mole), chloroform (100 ml.), and sodium methylenediamine, diethylenetriamine, triethylenetetraacetate (2 g.) was stirred while adding dropwise 38 g. mine, cyclohexanebismethylamine, etc. (0.20 mole) of a 40% acetic acid solution of peracetic The following examples will serve to illustrate further acid over a period of mins. The temperature was mainthe manner of practicing the invention. tained at 20-28 C. using external cooling as necessary Example 1' 4 methylenecyclohemnemethyl phthalate during the addition of the peracetic acid and for 2 hrs.

thereafter. At this time, more than 95% of the peracetic 35 acid had reacted. The mixture was washed with 100 ml.

GHFCHB CECE, of water and was then neutralized with 5% sodium bicarbonate solution. The chloroform was removed under CHFC /CHCH:40-(lf g-D z 0:011 reduced pressures leaving the solid epoxy ester. The prod- OHg-OH, o o CHzCHg uct weighed 3.5 g. and was found to contain 7.0% oxirane A t of 11th anh d 222 1'5 oles 40 oxygen. The calculated value for oxirane oxygen in a fi g g f s g i g & i mots) blS[1- oxasp1ro(2.5)oct-6-yl methyl]terephthalate 1s xylene 300 ml.), and titanium butoxide 0.1 g.) was refluxed and the water formed during the reaction was Example 3Diepoxide of 4-methylenecyclohexanemethyl removed using a suitable trap. A IS-in. fractionating adipare CHE-CH2 GHQ-CH3 CEa/\ /CHOH2O(|3CH2CH2CH2OH2O OHzCH /O -\OH O OHz-CHa i) O CHzCH: O/

column, packed with glass rings, was placed between A mixture of 4-methylenecyclohexanemethyl adipate the pot and the trap. The column had sufficient pres- (650 g., 1.8 moles) and sodium acetate (35 g.) was stirred sure drop to bring the pot temperature to 160-170 C. while adding dropwise 696 g. (3.7 moles) of a 40% acetic during the reflux period. After 10 hours, 27 ml. of solution of peracetic acid over aperiod of 2 hours. Exwater had been collected and the residual acidity was 0.7% ternal cooling was used when necessary to keep the tem- (calculated as phthalic acid). The mixture was allowed perature at 2025 C. during the peracetic acid addition to cool and 700 ml. of hexane was then added. The soluand for 3 hours thereafter. More than 95% of the tion was neutralized with 5% sodium bicarbonate solution peracetic acid was consumed during this period. Chloroand was then washed with two l000-ml. portions of form (1 l.) was then added and the mixture was washed water. The low boilers were distilled by heating up to with 1500 ml. water. The organic layer was neutralized 150 C. at atmospheric pressure; their removal was comwith 5% sodium bicarbonate solution and was then washed pleted by gradually reducing the pressure to 1 mm. and with two-1200 ml. portions of water. The chloroform raising the temperature to 175 C. The residue (55 6 g., solution was dried over sodium sulfate. The chloroform 97% conversion) was 4-methylenecyclohexanemethyl was then distilled under reduced pressure to give 656 g. phthalate of suificient purity for the subsequent epoxidaof a white Waxy solid; oxirane oxygen (found): 5.6%

tion process and for the preparation of the desired resins. (calcd.): 8.1%.

The above example is to be considered illustrative of the preparation of the other intermediate unsaturated Example 4-Diepoxide f 44716171)leneqclohexanemethyl esters coming within the scope of the invention. The con- Phihalafe ditions may be varied to some extent. For example, reaction temperatures in the range of 140200 C. lead The epoxldanon of 4'methylenecyclohexanemethyl to Products f gcod color and give practical reaction phthalate with peracetic acid was carried out using the rates with titanium alkoxide catalyst. Titanium butoxide pl'c'cedum described in Example Flom 495 of the is an excellent catalyst for the reaction at a concentration unsaturated ester, 491 gof a Viscous Colorless Oil s 0 level of 0.0050.l%. Higher concentrations may be used tained. The oxirane oxygen content of the product was but are generally unnecessary. The use of other similar ti- 5.9%.

Example 5 .-Diepxide of 4 -methylenet'yclohexanemethyl 1,4-cycl0hexanedicarb0xylate Using the procedure disclosed in Example 2, 4-methylenecyclohexanemethyl l,4-cyclohexanedicarboxylate (57 The mi ture wa cu d b hea in t 115-1 0 r was epoxldlzed Wlth 9 peracen? ac1d.(60 12 hour A hajd in f usible resi n via: obtained C f0 product (55 g.) was a white waxy solid having an oxirane oxygen content of 6.4 oxirane oxygen (calcd): 7.6%. Example 8 The above Examples 2, 3, 4 and 5 are to be considered as illustrative of the other epoxides of the invention. A The diepoxide compound (39.5 g.) used in Example suitable diluent may or may not be used. Peracetic acid 7 was mixed with maleic anhydride (6.9 g.) and 1,2,6- is an excellent epoxidizing agent, but other peroxy c'omhexanetriol (1.0 g.). This mixture cured to a tough pounds, which are well known in the art, may also be composition after heating for 18 hours at 120 C. used. The following structures represent other epoxides E I that were prepared by these procedures: m 6 9 CHFOHz A mixture of the diepoxide from 4-methylenecyclohexanemethyl l,4-cyclohexanedicarboxylate (60 g.), @U F: -*7 phthalic anhydride 15 g.) and 1,2,6-hexanetriol 1.5 g.) 0 OHz-CH: O n was heated at 130 C. for 12 hours and then at 180 C.

20 for 4 hours. A hard infusible resin was produced. wherein 3Or4 In place of the maleic anhydride, there can be sub- Examples of this group are the epoxidized methylenecystituted in above Examples 6 and 8 any other of the menclohexanemethyl esters of o-phthalic, isophthalic, tertioned anhydrides such as phthalic anhydride, 1,2-cycloephthalic,trime1litic, and pyromellitic acids. hexanedicarboxylic anhydride, etc. and any of the other CH CH mentioned polyols to give generally similar epoxy resins.

2 In place of the diethylenet-riamine, there can be substi- (300112011 2 tuted in above Example 7 any other of the mentioned l, n polyamines to give resinous epoxy products of generally similar characteristics. All of the epoxy resins of the Where 4 invention, as previously indicated, are especially valuable Examples of this group are the epoxidized methylene. for coating compositions, potting compositions and castcyclohexanemethyl esters of cyclohexane polycarboxylic 111g materlals- For p n employing thesle resin acids such as 1,2, cyclohaxanedicarboxylic acid, 1 2 3- compositions as coating materials, the compositions which cyclohexanetricarboxylic acid and l,2,3,4-cyclohexanetetare in liquid form are pp to The Surface desired racarboxyfic acid The Symbol indicates that h be coated and cured under the influence of either heat ringis fully hydrogenated or catalyst or both. Polymerization and cross-linking CH CH CH occur with the result that a hard, infusible and insoluble 2 2 2 coating is produced. Similarly, when these resin comgP CHCHZOfiJFOHQmfifOOHtCH positions are applied as potting compositions or as cast- 0 OHFGH, o O g, Q 40 ing materials, the same phenomena of polymerization Where and cross-linking takes place to produce the desired hard,

infusible material required. The epoxy resin composi- These BStfirS are deflvatlves 0f anfanedlolfflclds l f tions produced from the epoxides of this invention also il s rat fllflhf, for p Wlth 5116911116 Plmehc have excellent adhesive properties, adhering particularly acids. well to surfaces of glass and various metals.

GHFCH, CH -CH; The invention has been described in detail with particular reference to preferred embodiments thereof, but

E 7 /GHCHZOFCH CHOOCH2C it will be understood that variations and modifications 0 OHTGHI O O CHZ'OHZ O can be elfected within the spirit and scope of the inven- The epoxidized methylenecyclohexanemethyl esters of tion as hereinabove described and as defined in the maleic and fumaric acids comprise this group. appended claims.

In addition to the above compounds, the epoxidized What we l i i 4-methylcyclohexanemethyl esters of 4,5-epoxy-1,2-cyclo- 1. An epoxide selected from the group consisting of hexanedicarboxylic acid and diglycolic acid are included. those represented by the following general formulae:

CH: CHzCH2 on CH-COOHzCH CCHI gigs? n 1( O )n o I l o GHz-CH: o R (COOA) I CH2CH1 R3 2 OH err-common CCH: R4(COOA)2 ll and O o CHPCHZ 0 R5(COOA)2 GH OHz C r Hz CH2C CHCHzOCCHzOCHzCOCHzCH /C\-/GH| \O/ CH2CHz 0 CHn-CH2 0 Example 6 5 Example 7 The diepoxide from 4-methylen'ecyclohexanemethyl adipate (40 g.) was mixed with 3.2 g. diethylenetriamine.

wherein n represents an integer of from 2-4, each A rep- The diepoxide from 4-methylenecyclohexanemethyl resents the group:

terephthalate (41 g.) was added to maleic anhydride (7 g.) heated to a temperature of 90 C. 1,2,6-hexanetriol (0.9 g.) was then added and the mixture was heated to C. A hard infusible resin was obtained after heating at 115 C.

7 R represents a polyvalent benzene nucleus, R represents a polyvalent cyclohexane nucleus, R represents a 7-oxabicyclo[4.1.0]heptane nucleus, R represents a divalent alkylene group of from 2-12 carbon atoms, R represents a R OR group wherein each R represents a divalent alkylene group of from 2-4 carbon atoms and R represents a -CH=CH group.

2. An epoxide represented by the general formula:

wherein n represents an integer of from 2-4, A represents the group:

CH:CH2

and R represents a polyvalent benzene nucleus.

3. An epoxide represented by the general formula:

R (COOA) wherein n represents an integer of from 24, A represents the group:

CHFCHB (HITCH? and R represents a polyvalent cy-clohexane nucleus.

4. An epoxide represented by the general formula:

f zt An wherein A represents the group:

GH -0H and R represents a 7-oxabicyclo[4.1.0]heptane nucleus.

5. An epoxide represented by the genera-1 formula:

R (COOA) wherein A represents the group:

OH 0H,

and R represents a divalent alkylene group of from 2-12 carbon atoms.

6. An epoxide represented by the general formula:

R (COOA) wherein A represents the group:

CH2CH5 4 References Cited by the Examiner UNITED STATES PATENTS 2/ 1951 Niederhauser 260-348 8/1954 Foster.

WALTER A. MODANCE, Primary Examiner.

N. S. MILESTONE, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,288,814 November 29, 1966 Wayne V. McConnell et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, line 40, for "-ROR-" read R -O-R column 4, line 39, for "3.5" read 35 column 5, lines 55 to 62, the formula should appear as shown below instead of as in the patent:

CH -CH I Signed and sealed this 7th day of November 1967.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

1. AN EPOXIDE SELECTED FROM THE GROUP CONSISTING OF THOSE REPRESENTED BY THE FOLLOWING FORMULAE: 